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Sostmann

OF

THERMOMETRY I

1: THE

ABSOLUTE,

OR THERMODYNAMIC

KELVIN,

TEMPERATURE

SCALE

Temperature is a measure of the hotness of something. be rational (and useful between people), there must scale of numerical values (the most familiar of which Centigrade

VdUfZS.

Scale),

and

on

devices

for

interpolating

only

temperature

scale of

with

a real

basis

in

nature

is

the

the * mark), and since it reference point is needed to was chosen, in the original

273.15K,

OC is a temperature with which we all have a common experience. It is the temperature at which water freezes, or, coming from the other side, ice melts; at which water exists under ideal conditions as both a liquid and a solid under atmospheric pressure. In 1954 the reference point was changed to a much more precisely reproducible point, O.OlC. This is known as the triple point of water, and is the temperature at which water exists simultaneously as a liquid and a solid under its own vapor pressure. The triple point of water will be the subject. of extended discussion important in a later reference article in this series point in thermometry. of articles. It is the most

The unit of temperature temperature interval K, and C or K (the indicate a temperature 1K or lC, but the

of the TKTS is the kelvin, abbreviated K. The C is identically equal to the temperature interval latter without the symbol) may be used also to interval. The difference between 1C and 2-C is 1-C = the temperature 274.15K.

temperature

Measurements of temperature employing the TKTS directly are hardly suitable for practicable thermometry. Most easily used thermometers are not based on functions of the First and Second Laws. The practicable thermometers that will be discussed later in this series of articles depend upon some function that is a repeatable and single-valued analog

of, or consequence of, temperature, and they are used as devices of utilitarian temperature scales (such as the Temperature Scale) which are themselves artifacts. The main the realisation of the TKTS is to establish relationships Thermodynamic Scale of nature and the practical thermometers of the laboratory or of industry, so that made by non-thermodynamic means can be translated into TKTS, and rational temperature scales can be constructed related to real&able physical phenomena. There points. two or ture is exist in nature a number These are physical states three of the three possible constant. of in what which phases

A two-phase equilibrium is represented by the earlier example of the freezing point of water, or, more properly, the coexistence of liquid and solid water. For this equilibrium to represent a constant temperature, OC, pressure must be specified, and the specification is a pressure of 1 standard atmosphere, 10 1325 Pascal. (A two-phase fixed point at 1 standard atmosphere is called the normal point). The variation due to pressure from the defined temperature of a liquid-solid equilibrium is not large (which is not to say that it may not be significant). The freezing point of water is reduced approximately O.OlK for an increase of pressure of 1 atmosphere. The variation due to pressure for a liquidvapor equilibrium is relatively very large. A three-phase equilibrium is represented by the triple point the coexistence of liquid and solid water under its own vapor at 0.Ol.C. Because all three possible phases are determined physical state, it is generally possible to realise a triple point curately than a two-phase point. This may be seen from the Phase Rule of Gibbs: of water, pressure, by the more ac-

P-C-2=F where P is an integer equal to the number of phases present, C is the number of kinds of molecule present (for an ideally pure material, C = 1) and F is an integer giving the number of degrees of freedom. Obviously, for the two-phase equilibrium there is one degree of freedom, pressure, and for the three-phase equilibrium F = 0; that is, the temperature is independent of any other factor. Fig.1 illustrates one, two and three-phase equilibria.

3a

Fig. 1: The Phase Rule of Gibbs. P = the number of phases C = the number of components (1 for a pure material); degrees of freedom. la is uncontrolled. lb is a melt point. Ic is a triple point. A typical since the (or rather device for realizing the TKTS is vapor pressure of an ideal gas a statistical mechanical function, transfer function in pressure of of a gas a gas kept

the helium gas thermometer, is a thermodynamic function which for the purpose is the thermometer at constant may be volume, chosen or the

change in volume of a gas kept at constant to measure accurately change in pressure in volume, constant-volume gas thermometers than constant-pressure gas thermometers. A rudimentary gas illustrated by using low the temperature Celsius Scale.

pressure. Since it is easier than it is to measure change are more common in use

be bethe

Fig. 2 shows a cylindrical bulb of constant volume, connected by tubing defined as constant-volume, to a U-tube manometer. A second connection to the manometer leads to a reservoir of mercury, which contains a plunger, P, by means of which the column height of the manometer may be varied. The constant-volume bulb and tubing contain an ideal gas.

The bulb is first surrounded by an equilibrium mixture of ice and water (C, in Fig 2a). When the gas is in thermal equilibrium with the slurry in the bath, the pressure of the gas is adjusted by moving the plunger so that both columns of mercury in the U-tube are at the same height, corresponding to an index mark 1.

2a Fig.2: A rudimentary gas thermometer. B = mercury, C = water t ice (O-C), (100(Z), P = a plunger for adjusting A = helium gas. D = water t steam mercury level.

2b

Next, the ice bath is removed and replaced with a bath containing boiling water, or more correctly, an equilibrium mixture of liquid and vapor water at a pressure of 1 standard atmosphere, (D, in Fig 2b). As the manometric gas is heated by the boiling water it expands, and the mercury in the manometer is displaced. The plunger is actuated to reposition the surface of the mercury in the left leg at the index mark 1, restoring the criterion of constant volume in the closed gas system, a condition shown in Fig 2b. However the mercury in the right, open leg is not now at the index mark 1, but measurably higher. In fact, the difference in heights indicates that the pressure of the enclosed gas at the boiling point is 1.366099 times the pressure at the freezing point. We can then calculate: (100-c - OC)/(1.366099 - I) = 273.15 Eq.2

this we can understand ratio change between by 273.15 Celsius or reached therefore + 273.15 on the temperature reference which is the and 273.15K,

the Celsius degree OC and 1OOC. Thus kelvin intervals below zero of the TKTS. The

T = t

Eq.3 TKTS and t is temperature interval and the zero to the properties of on the Celsius of the TKTS have any specific sub-

where T is temperature Scale. Note that the been defined without stance. All terms constant of the P2 Ts the volume equation

gas

thermometer

measurements

can

be

expressed

in

PI /

where Scale, This that sure the and

= 01 - To) /

are TOs temperatures are the

(5

- To)

on the that TKTS, Scale. will the natural

Eq.4 temperature

zero

of

an ideal gas. The reader reflects Charles or Boyles gas, respectively, be held

gas is a gas whose behavior can be predicted exactly from Charles Law, which obeys it through all ranges of temperature sure, and where the relationship between concentration (n/V), temperature (n/V)(T/P) more commonly PV = nRT where R is the gas constant, identical for all ideal gases. and is known to about 30ppm. A second condition is that thus the internal energy, intermolecular forces acting, depend on the molecular distances, and (6E Unfortunately is a large / 6V)T = 0 is no real ideal gas, Helium comes closest, and the carbon uncertainty dioxide and absolute = I/R written pressure = a constant as is

Eq.5

there number.

real a in

approach in of

as Since zero

their

pres-

a gas

zero

volume)

requirement

an ideal gas is approached by making a number of measurements at a number of pressures and extrapolating to zero pressure. Such a system of measurements is shown in Fig. 3. Regardless of the nature of the gas, all gas thermometers at the same temperature approach the same reading as the pressure of the gas approaches zero.

374.0

gases at various point of steam. of the ideal gas law used, in to ac-

have

modifications

count for the non-ideality of real gases. of Clausius, is the virial equation, which of the density of the gas, and is written: nB, + -- n2Cv + ---2 B, n3Dv + ---3

is much expansion

that terms

PV = nRT(1

+...)

Eq.8

where

the

coefficients

C, D, etc.,

are

called

the

second,

third,

fourth,

etc., volume virial given temperature. mometry, it is coefficient. The departure accurate gas

are constants for a given gas at a range of gas densities in gas therto go beyond the second virial

from

ideality

is

only

one

of

the

problems

of

A second is the purely mechanical matter a real connection to convey the pressure ter. It is inconvenient to locate the bulb thermostatted enclosures, 2 to illustrate enclosure, and a common each carefully thermostatted. this configuration.

of dead space. There from the bulb to the and the manometer in practice Fig. is 4 is to use two a modification

Fig.4: Thermostatted gas thermometer. meter and the gas bulb are separately temperature; the (long, perhaps many is not. The length, price which paid is that goes through is The there the is a capillary wall of each

some and

relative to the capillary volume. capillary length can be measured at suitable intervals. The capillary volume can be kept small by providing a capillary of small diameter, but not so small as to introduce thermomolecular pressures where the tube a correction for passes through a temperature gradient, or , conversely, thermomolecular pressure can be made.

A third

obvious

problem

is that

of

the

thermal thermal

expansion gas

of

the

materi-

the whole system is subject or estimated, and for which correction the system, required including effects from is that for

changes, which must be made. head itself. impurities in clean system, pressure

A fourth gas in

of

the

of

the

to the remaining

in which ideally

the are

gas, ab-

sorbed on the walls of the bulb and other parts of the thermometer system at the reference temperature, desorbed at a higher temperature, with the effect of elevating the measured gas pressure, and then reabsorbed as the temperature approaches the references temperature. Attention to the elimination of sorption has resulted in gas thermometry measurement Gas thermometry for some Edsinger, of the has normal claimed boiling the point attention of water of a as 99.975-C! of fine experi-

number

generations, followed

dards. This work forms much of the Practical Temperature Scale of 1968 Scale of 1990, in an effort to more

temperatures in a practicable Scale. A concise mometer and gas thermometry at the NBS is should be consulted by anyone interested Schooley provides an example of the accuracy work: Fixed point IC Steam pt Gas therm IC 99.975 231.924 419.514 IPTS-68 3 100.000 231.9681 419.58

account of the gas therand given by Schooley, in experimental elegance. and precision of this

Uncertainty

Tin pt Zinc pt

With the conclusion of work in preparation for ITS-90, is considered to be a finished matter at the NBS. The itself, which should have been preserved as a national ment, is now in the process of dismemberment. As a generality, namic values methods have gas the thermometry thermometric used largely has led the fixed points, to check its

of

been

include

acoustic and of

thermometry,

dielectric-constant each

gas

thermometry, to a

appropriate

2: THE

SCALE

OF

1990

International

a recommendation of its Consultative new practical temperature scale, Temperature Scale of 1968, which of previous Scales, those of 1948,

Committee

Thermometry

to replace the International had replaced, in turn, a suc1927, etc. The official text of of as word French, 1990. of will The be pubITS-90 is 1990. is is not de-

the ITS-90, in English translation lished in Metrologia, probably in officially in place as the international

1 January,

As in previous practical used in the title of the fined as tr,O/C and temperatures = TgO/K are -

substances (defining~ fixed points), interpolating instruments, and equations which relate the measured property to T(90). The defining fixed points and the values assigned to them are listed in Table 1, and the values which were assigned on IPTS(68) are listed also, for comparison. It is to be remembered that, while the Scale values assigned to a fixed point may have been changed, the fixed point has the identical hotness it always Several had. deep From device From 3.OK to the triple volume gas thermometer From gas From 3.OK thermometric to the gas triple point of neon with 3He or 4He as the 4.2K to the triple point of neon (24.5561K) using a constantcryogenic 0.65K to ranges 5.OK using are a provided. helium These vapor are: pressure interpolation

point

of

neon

with

4He

as

the

thermometric

10

These ranges cialists, and thermometer from 13.8033K of The subranges. below Scale slightly

are probably of interest to only a limited number of spewill not be dealt with in detail in this paper. The resistance portion of the Scale is divided into two major ranges, one to 0-C and the other from OC to 961,68C, with a number There to is third above short OC, in range Table which 2. embraces -38.8344 temperatures to +29.7646-C. slightly are specifically

ranges

summarised

The interpolations platinum resistance the resistance WT(90) a change OC, and one from at the

as the ratios of the (PRTs) at temperatures water; that is: Eq.10 of IPTS(68) which be used the

resistance of T(90)

of and

resistance

at

as denominator. The PRT must free; it is considered a measure two constrains are met: L 1.11807 L 0.844235 for use (gallium (mercury to the melt triple freezing

W(302.9146K) W(234.3156K) and a PRT acceptable meet this requirement: W(1234.93K) The ship: temperature

Z 4.2844 T(90) is

(silver calculated

point) resistance

W,T(90)

cific PRT from the reference function at T(90). (The reference functions represent the characteristics of a fictitious standard thermometer; the deviation function represents the difference between that thermometer and an individual real thermometer). The deviation function is obtained by calibration at the specified fixed points, and its mathematical form depends THE upon the temperature 13.8033k range TO 273.16K of calibration.

RANGE

FROM

11

The

reference

function 12

for

this

range

is

ln[WrT(90)]

= A,

+ K Ai{[ln(T(90)/273.16K)+1.5]/1.5)i i=l of A, and Ai are over given the or in the text range, of

Kq.15

where If the

the PRT

values is to

the down

Scale. to 13.8033K,

be

calibrated

it must be calibrated at specified fixed tures determined by vapor pressure mometers will most likely be calibrated and this paper will of general interest 83.8058K (-189.3442-C), not to the include details, the primary triple point

The subrange from -189.3442 to 273.16-C triple point of argon (-189.3442C), the 38.8344-C) and the triple point of water to b. The deviation FROM function I] 0-C is: lllnW(T(90))

requires calibration at the triple point of mercury (obtain the coefficients a and

+ blW(T(90)) TO 961.76.C

Eq.16

from OC of silver,

point

of

water

to

the

WrT(90)

= C,

754.15)/4811i

Eq.17

and

the

coefficients

Ci are

specified

in

the

text

of the

over this entire range must be calibrated at and the freezing points of tin, zinc, aluminum a, b and c are derived from the tin, zinc and the reference below coefficient value at the

aluminum calibrations respectively, the deviation of WT(90) from the silver. For d = 0. The dWT(90) temperature deviation II3 measurements function is 11 + b[WT(90) + dCWt(90)

freezing

= a[WT(90) + c[WT(90)

II2

Eq. 18

- W(933.473KE2

12

PRTs

may

be

calibrated

over

the

whole

range

or

for

ranges shorter

terminating ranges of

at the freezing points Eq. 18, the equation is jJoner Aluminum Zinc limit

For

the

still

shorter

range

from

the

triple

point

of

water

to is:

the point

at the deviation

Eq.19 of water triple function to the freezing of water point and of the

indium, freezing dWT(90) For the gallium, equation For the gallium

the

point is:

triple point of water to required at these points, Eq.20 except for the

calibrations are gallium melting dT(90) However portion 0-c. For a = aCHT(90) the of the

required at the mercury point, and the deviation 11 + bCWT(90) function below OC, must and 112

reference Scale

for

relatively

simple

thermometer range from 1.5mK below, see the article Isotech Journal.

13

The

temperature thermometer

range as

above

the

freezing

point

of and

silver the

employs relationship

radiation is:

interpolating

instrument,

L X(TYD)/LX(TYO(X)

= (expCc2/

XT90(X)]

1) 1)

Eq.22

the spectral concentrations of radix in vacuum at TSO and at TSO(X). gold point or the copper point. C2 =

3: THE

1990

VALUE

OF

THE

OHM of the standard ohm also change effect, of the in the slight 1990. new but

The National The change international not insignificant various national resistors following Germany:

because resistance,

the ohm by the of the standard The resistance. States and West

NPL (England) increased the value of their ohm by t1.61 ppm. Thus a perfectly stable 1 ohm resistor calibrated at NPL prior to January 1, 1990, has a new value of 0.99999839 ohm. A 10 ohm resistor has a new value of 9.9999839 ohm. 1Q (NPL 1Q (NPL NIST ppm. 1990, value 90) 89) (United = 1.00000161Q = 0.99999839Q States) (NPL (NPL 89) SO) the value of their ohm by +I.69

increased

1 ohm resistor calibrated value of 0.99999831 ohm. ohm. = 1.00000169s2 = 0.99999831Q (NBS (NIST 89) 90)

at NIST A 10 ohm

prior to resistor

1~ (NIST 1Q (NBS

Germany) increased the 1 ohm resistor calibrated value of 0.99999944 ohm. ohm.

value of their ohm by to.56 at PTB prior to January 1, A 10 ohm resistor has a new

14

1~ (PTB 1Q (PTB

as follows: tL92ppm. VNIIM (USSR) -0.15ppm

Other laboratories adjusted the ohm (a decrease); France, +O.?lppm; BIPM, The effects on calibrated the calibration by in 1989, and at of with 650-C

a standard a typical (f or

therOC as are

mometer

25.5249052)

t(89)

0-c

650-C where d(Q) and d(t) is

NBS 89 Q

NIST

90 Q

25.52490 85.28842

is the decrease the increase in

25.52486 85.28828

1 1 t a(tl 13 are

a and

is

conventionally

reported

at

25-C,

and

will

con-

t(90) of the ohm may be significant that the difference in the value resistor will require consideration.

************************************+***%%%%%%%%%%%%%%%%%%%% In our next issue, the fixed points realising them. we and will of discuss in detail the the equipment and physical operations embodiment involved of in

TABLE 1 FIXED POINTS OF THE IPTS-68 AND OF THE ITS(90) SUBSTANCE AS ADOPTED BY CIPM, OCTOBER 5 1989 CELSIUS TEMP. ITS-90 -259.3467

-218.7916

15

STATE CELSIUS TEMP. IPTS-68 Trip Trip Trip Boil Trip Trip Melt Freeze Freeze Freeze Freeze Freeze Freeze Freeze -259.34 -218.789

-189.352 -195.802 -38.842 0.01 29.772 156.634 231.9681 419.58 660.46 961.93 1064.43 1084.88

e-H2

02

Ar

N2 Hg H20 Ga

-189.3442 -195.794

-38.8344 0.01 29.7646 156.5985 231.928 419.527 660.323 961.78 1064.18 1084.62

in points

equilibrium are

between

the

ortho

and

para

at 1 standard

atmosphere

= 101 325

TABLE 2 RANGES OF THE ITS-90 THE PURCHASEROF A CALIBRATION MUST STATE THE RANGE REQUIRED*

LOW LIMIT -259.3467

16

e-H

32

(TP),

e-H2

(VP),

Ne (TP),

(TP), Ar (TP).

Hg

Hg (TP), H20

-218.7916

0.01

02

(TP) -189.3442

0.01

Ar

H$

(TP), (TP),

OF), Ga (ME)

Hz0

(TP)

0.01

0.01 0.01

H20 (TP).

H20 H20 (TP),

Ga (HP).

Ga (HP),

In (FP)

Sn (FP)

231.928

419.527 660.323

(TP).

Sn (FP),

Sn (FP),

Zn (FP)

2n (FP), Al

0.01

961.78

Zn (FP), Ga (MP)

(FP) at

Al

-38.8344

29.7646

pressure determination, (TP) = triple point. (VP) = a vapor (MP) = melting freezing point at 1 standard atmosphere, standard atmosphere *The purchaser may choose to specify -189.3442 to +419.527, for example, -200 to +500. example,

=

1

point

ranges, for

17

TABLE 3 THE COEFFICIENTS OF THE REFERENCE The values of the coefficients Eq. 15 and 17 Eq.15 CONSTANT OR COEFFICIENT VALUE FUNCTIONS functions of

347 29

A0

Al A2 A3 A4 A5 A6 A? A8 A9 A10 All A12

-2.135 3.183 -1.801 0.717 0.503 -0.618 -0.053 0..280 0.107 -0.293 0.044 0.118 -0.052

247 20 435 97 272 04 440 27 993 95 323 22 213 62 152 24 028 65 598 72 686 32 481 34

co

Cl c2 c3 c4 c5 c6 c7 c8 C

2.781 1.646 -0.137 -0.006 -0.002 0.005 0.001 -0.002 -0.000 0.000

572

54

e-H2 (TP) Ne UP) 02 (TP) 0.001 0.008 0.091 0.215 0.844 1.000 190 449 718 859 142 000 07 74 04 75 11 00

In (MP) 1.118 1.609 1.892 2.568 3.376 4.286 138 801 797 917 008 420 89 85 68 30 60 53

Ar (TP)

Hg (TP) Hz0 (TP)

nP (FP)

18

OF

PART

Th-o&y, thermometry

at

Twnpm

a, Academic

London

and

New

York

(1873)

F. Henning, H. Maser, Twnpucatuwn &wag, New York, 3rd edition (1977). German pressure thermometry by W. Thomas THE INTERNATIONAL Preston-Thomas 06 19 68 TEMPERATURE The (~e:ev-i-&on SCALE

t&&a

Ira.tea~od 04 1975

I Metrologia tie

P.wzc-GcaX Tanpeaduae 12, 1 (1976) the EPT-76, France. This at some future

Supp&mentcMy Inbomon Bureau International des publication continues to be date to include ITS-90

4oa

Poids valuable, et

R. E. Bedford, G. Bonnier, H. Maas, F. Pavese, appeoximetlng .#LQ I-tied Temp wt.aauAe BIMP, when published; no projected date is known. unofficial copies of a late draft indicate that this will e Scu& The Iti.awat.Lod TempcauUu/t official text of the new Scale, and it will Metrologia advises that it will be published 1990). THE 1990 OHM Ln tie Vdue 04 the UK Force and Redistance, England (1989) al, the NIST Technical New Rep~eaentetLon-6 of Commerce (1989) Neue Iwoti (1989) Re&xence National 06 be in

S+and4nda Physical

06 &&QCLaboratory,

Note

1263,

04

.the

40~ .the

d.-k

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